Sulphuric acid derivatives of organic acid amides



Patented June 14, 1938 UNITED STATES PATENT OFFICE SULPHURIC ACIDDERIVATIVES OF ORGANIC ACID AMIDES Erich Rosenhauer,

Dusseldorf-Benrath, Germany, assignor to the firm Henkel & Cie, G. 111.b. H., Dusseldorf, Germany many May 12, 1933 7 Claims.

It has been found that a new class of valuable substances may beobtained by treating with sulphonating agents amides having at least onegroup capable of being sulphonated, of the general formula Z.X.R.NY,where R signifies an aliphatic carbonyl or aliphatic sulfonyl group, X anon-metallic polyvalent atom of the group consisting of oxygen, sulphurand nitrogen, Z an aliphatic, cycloaliphatic or aromatic radicalcontaining not more than carbon atoms and NY an amido group substitutedby at least one higher, non-aromatic hydrocarbon radical Y containing atleast 6 carbon atoms.

This application is a division of my United States application forUnited States Letters Patent, Serial No. 722,686, filed April 27, 1934,entitled Sulphuric acid derivatives of organic acid amides.

For the process according to the present invention, amides, substitutedat the nitrogen, of aliphatic oxymercapto or amino carboxylic orsulphonic acids, substituted at the oxygen, sulphur or nitrogen areemployed as starting substances.

The following general formulae may be proposed for these compounds:

(1) Z.O.R.N'Y (2) Z.S.R.N'Y (3) Z'.Z".N.R.NY

The compounds according to Formulae 1 and 2 constitute amides ofsubstituted oxy or mercapto acids, and those according to the Formula 3constitute amides of secondary or tertiary aminoacids, which may containthe amino-nitrogen combined in any desired manner, for example insecondary, tertiary or ring form. In these derivatives of amides, theorganic radicals Z, Z and Z" signify aliphatic, cycloaliphatic andaromatic radicals. Suitable radicals are for example the ethyl,,B-oxy-ethyl, acetyl, cyclohexyl and phenyl radicals. R represents theradicals of methane, ethane, propane acids and their homologues, such aslauric acid, and also the radicals of the corresponding sulphonic acids,such as ethane, propane and octodecane sulphonic acids. The amido-groupNY contains higher aliphatic or cycloaliphatic hydrocarbon radicals.Such radicals are fatty alkyl radicals, such as the decyl and undecylradical, the dodecyl, tetradecyl and octodecenyl radical, as well as thecorresponding radicals of alcohols obtained by the reduction of othersoap-forming carboxylic acids, such as resinic acids and naphthenicacids. The said derivatives of amides contain a reactive group capableof being sulphonated. Such groups are free hydroxyl groups and carbondouble bonds.

The said reactive amides may be obtained for example by reacting halogenacyl amides, substituted at the nitrogen by a higher aliphatic or 5cycloaliphatic residue, with alcohols, mercaptans or primary orsecondary amines. Thus 04, p, 'ydioxypropyloxylaulric-N-cyclohexyl-amide is obtained froma-bromolauric-N-cyclohexyl-amide and the monosodium compound ofglycerol, 10 or fl-phenoxy-ethane-sulphonic-N-methyldodecyl amide fromp-chlorethane-sulphonic-N-methyldodecyl amide and sodium phenolate.Furthermore, tolyl-mer-capto-ethane sulphonic-N-hexadecyl-amide isobtained from bromoethane-sul- 15 phonic-N-hexadecyl-amide and sodiumtolylmercaptan. In a similar manner, anilino-acetic- N-undecyl-amide isobtained from monobromacetic-'N-undecyl amide and aniline. Finally, thestarting substances for the present process may so also be obtained bythe reaction of organic oxy, mercapto or amino acids, which aresubstituted at the oxygen, sulphur or nitrogen by an organic radical,with higher aliphatic or cycloaliphatic primary or secondary amines. Inthis case the acids are employed as such or in the form of theirfunctional derivatives, such as esters, anhydrides, acid halides,lactones and the like. By this process, for example,phenyl-amino-acetic- 30 N-cyclohexyl-amide is obtained fromphenylamino-acetic-methyl-ester and cyclohexylamine, and(oxyethoxy)-acetic-N-undecyl-amide is obtained from the lactone of(oxy-ethoxy) -acetic acid and undecylamine. 35

According to the nature of the organic radicals and the sulphonatingagent both true sulphonic acids and also sulphuric esters are formed intreating the amides described with sulphonating agents; some of thestarting substances absorb 40 both groups simultaneously. The sulphuricacid radical may enter both the amide group and also the acid group andthe organic substituents.

As sulphonating agents are employed: strong 45 sulphuric acid, sulphuricacid containing S03, S03 and its additive products with organiccompounds, chlorosulphonic acid and the like sulphonating agents, itbeing expedient to work in the presence of solvents, diluents anddehydrating agents, but 50 in some cases these may be omitted.

The water-soluble products obtained according to the present inventionmay be employed as soap substitutes, and also in the pharmaceutical andcosmetic industries. 55

Examples tuted at the nitrogen by higher aliphatic radicals is obtained.

42 parts by weight of the amide mixtureare. dissolved in 200 parts byvolume of ether-and 20 parts by weight of chlorosulphonic acid areadded.

at a temperature of to C. with good agitation. Agitation is continueduntil a test sample of the sulphonation product is clearly soluble inwater. After neutralization with soda and working up, the sodium saltsof the mixture of acid sulphuric esters of the higher oxy-ethoxyacetic--N-alkylamides are obtained in the form of a white powder which dissolvesin water to form clear solutions. The substance is absolutely stable tohard water and exhibits a-very' good foam-producing and wetting power.

(2) 20 parts by Weight of phenoxyacetic-N- cyclohexyl-amide are heatedon the'water bath for about 2 hours with the same quantity by weight ofconcentrated sulphuric acid. The reaction product is poured into icewater, is neutralized with soda and salted out with common salt. Theresulting sodium'salt of the monosulphonic acid ofphenoxyacetic-N-cyclohexylamide is, in the dry condition, a powder whichdissolves in water to form clear solutions.

(3) 20 parts by weight of a'mixture of the amides of phenoxyacetic acidand a mixture of higher aliphatic amines, which have been obtained fromthe amides of coconut fatty acids by Hofmanns reaction, are heated onthe water bath with the same quantity by weight of sulphuric acid forabout half an hour. The reaction product is poured into ice water,neutralized with soda and salted out with common salt. The resultingsodium salt of a mixture of sulphonic acids ofphenoxyacetic-N-alkylamides is a white powder which dissolves in coldwater to form clear solutions having a good foam-producing power.

I claim:

'- -1. An alkali-metal salt of sulphonated oxyfatty acid-amides whichare substituted at the amido group by a higher non-aromatic hydrocarbonradical containing at least six carbon atoms and at the oxygen by ahydrocarbon group containing not more than carbon atoms.

2. An alkali-metal salt of sulphonated oxyfatty acid-amides which aresubstituted at the amido group by a higher alkyl radical containingv atleast 6 carbon atoms and at the oxygen by a-hydrocarbon group containingnot more than 10 carbon atoms.

3. An alkali-metal salt of sulphonated oxyfatty-acid-amides which aresubstituted at the amido group by a cycloalkyl radical containing atleast 6 carbon atoms and at the oxygen by a hydrocarbon group containingnot more than 10 carbon atoms.

4. An alkali-metal salt of sulphonated oxyfatty acid-amides which aresubstituted at the amido group by a higher non-aromatic hydrocarbonradical containing. at least 6 carbon atoms and at the oxygen by anaromatic radical containing not more than 10 carbon atoms.

5. An alkali-metal salt of sulphonated higherhydroxyethoxyacetic-N-alkylamides.

6. An alkali-metal. salt of sulphonatedphenoxyacetic-N-cyc1oalkylamides.

7. An alkali-metal salt of sulphonated higherphenoxyacetic-N-alkylamides.

ERICH ROSENHAUER.

